Problem Set #4 KEY Chem 417

November 14, 2012 Due Friday November 30, 2012 Fall 2012

Solids and Transition Metal Complexes

1. Sketch cubic, body-centered cubic and face-centered cubic unit cells. How many atoms are
in each unit cell?

2. Describe what is meant by intrinsic and extrinsic semiconductors. Please give an example
of an intrinsic semiconductor and examples of extrinsic (doped) semiconductors of
different types. Explain how and why metals and semiconductors differ in their relationship
of conductivity to temperature.
3. Draw a Born-Haber cycle (roughly to scale) for the formation of MgBr2. Also show how
the problem is solved with a Hesss Law style summing of reactions. Determine the lattice
enthalpy of MgBr2 (Mg2+(g) + 2 Br(g) MgBr2(s)) by both methods (which should give
the same answer!).
Use the following data:
reaction H (kJ/mol)

sublimation of Mg(s) +148

ionization of Mg(g) to Mg2+(g) +2187

vaporization of Br2(l) +31

dissociation of Br2(g) +193

electron attachment to Br(g) -331

formation of MgBr2(s) -524

4. CaO is harder and has a higher melting point than KF. Both salts have the same type of
structure (NaCl structure). Explain the difference between the two salts.

5. Use geometry and the Pythagorean theorem to determine what percentage of space in a bcc
unit cell is filled by the spheres. (All spheres are the same size.)
6. Gas phase MnF3 adopts a distorted trigonal planar geometry such that one MnF bond is
shorter than the other two (C2v symmetry). In contrast, both CrF3 and FeF3 have trigonal
planar geometry (D3h geometry, all MF lengths equal, all FMF equal). The difference
for the Mn compound is attributed to the Jahn-Teller effect. Using the dorbital splitting
diagram for trigonal coordination (shown below) explain the underlying reason that MnF3
is not trigonal planar. Draw the d-orbital splitting diagram under C2v symmetry. (This
problem is very similar to a suggested textbook problem. For that problem, and this one,
consult the text on Jahn-Teller effect not covered in class.)
7. Six-coordinate transition metal compounds are usually found in an octahedral geometry,
but a few examples possess trigonal prismatic (or distorted trigonal prismatic) geometry.
What are the factor(s) that favor trigonal prismatic geometry in six-coordinate metal
complexes? How can one stabilize a complex in a trigonal prismatic geometry?
8. A pentacoordinate complex L5M is synthesized where L is a very large ligand. Explain on
steric grounds what is the favored geometry, trigonal bipyramidal or square pyramidal.

9. For which member of the following pairs of complexes would oct be larger and why?

(a) [Cr(H2O)]62+ or [Cr(H2O)6]3+

(b) [CrF6] 3- or [Cr(NH3)6]3+
(c) [Co(en)3] 3+ or [Rh(en)3]3+
(en = 1,2-diaminoethane)
10. For the following complexes, rationalize the number of unpaired electrons observed for
each complex:

Mn(CN)64 1 unpaired electron

Mn(CN)62 3 unpaired electrons

Pd(CN)42 0 unpaired electrons

CoCl42 3 unpaired electrons

NiBr42 2 unpaired electrons

11. Prepare a d-orbital energy level diagram for a square pyramidal complex.

12. Consider the following series of six platinum compounds.

number molecular formula # of ions

1 PtCl24NH3 3

2 PtCl23NH3 2

3 PtCl22NH3 0

4 PtCl22NH3 0

5 KPtCl3NH3 2

6 K2PtCl4 3

From the molecular formulas and numbers of ions produced when each compound is
dissolved in water, deduce the structural formula of each compound, being explicit as to
which ligands are in the coordination sphere. Draw structures for each platinum containing
molecule or ion. Note that compounds 3 and 4 are isomers (one is polar, one is non-polar).
All of the compounds have the same geometry at platinumwhat is that geometry?

all are square planar at Pt

13. The spin-only magnetic moment () of a transition metal complex is related to the number
of unpaired electrons in the complex as follows:

= {N(N + 2)}1/2B

N = number of unpaired electrons

B = Bohr magneton (a unit of measure)

The spin-only magnetic moment () of [Mn(NCS)6]4- is found to be = 6.06 B. Is

[Mn(NCS)6]4- a high spin or low spin complex?

14. Which of the following is the stronger acid? Which has the higher o? Briefly rationalize
your choices.

[Ru(H2O)6]2+ [Ru(H2O)6]3+
15. Provide clearly drawn structures for all isomers of the following octahedral complexes:
(a) triammineaquadichlorocobalt(III) chloride (3 isomers)
(b) tris(ethylenediamine)cobalt(III) chloride (2 enantiomers)

16. The tetradentate chelating ligand P(CH2CH2PPh2)3 (shown below as a structure and in
simplified cartoon form) was used to make some cationic five-coordinate compounds of
palladium. The fifth coordination site was occupied by a Lewis basic ligand like pyridine.
Abbreviating the tetradentate ligand as PP3 and using L to represent the other ligand, a
general representation of the ion is: [(PP3)Pd(L)]+

P P
PPh2 P
Ph2P
Ph2P P P

Generally, when five-coordinate compounds are formed, two geometries are typically
observed: square pyramidal and trigonal bipyramidal. Of these two, which one is more
favorable on steric grounds? How can you justify your answer?
Draw sketches of how the species [(PP3)Pd(L)]+ would look in a square pyramidal geometry
and in a trigonal bipyramidal geometry. Do you see symmetry differences? Would they have
a different number of 31P signals in the 31P NMR spectrum? Shown below is an example 31P
NMR spectrum for one of these species. The integration of the two peaks is in about a ratio
of 3:1. Knowing how to interpret the chemical shift position is not required. Number and
relative integration of signals tells the whole story here. With this information, make an
argument for one geometry over the other. Show that the NMR spectrum is consistent with
one of the geometries and inconsistent with the other one.